Titania-polyamide nanocomposite formed by in situ polymerization

ABSTRACT

A method for making a titania-polymer nanocomposite by simultaneously forming TiO 2  nanoparticles in situ from a TiO 2  precursor in the presence of urea and interfacially polymerizing polyamide precursors thereby producing a titania-polymer nanocomposite. A titania-polymer nanocomposite made by this method. A method for removing a dye or metal from water comprising contacting contaminated water with the titania-polymer nanocomposite.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application No.62/886,624, filed Aug. 14, 2019, which is incorporated by reference forall purposes.

STATEMENT REGARDING PRIOR DISCLOSURES BY THE INVENTOR OR A JOINTINVENTOR

Aspects of this technology are discussed by Ali, et al., J. MolecularLiquids 269: 564-571, available online Aug. 14, 2018 which isincorporated by reference for all purposes.

BACKGROUND OF THE INVENTION Field of the Invention

The invention pertains to simultaneous removal of contaminants, such asdyes and toxic metals, from wastewater water using titania-basedmaterials.

Description of Related Art

Contamination of water, including industrial waste water, with dyes andtoxic heavy metals is a serious environmental problem. Synthetic dyes,such as those used to impart color during the manufacture of textiles,paper, plastics, or cosmetics, are very stable and difficult tobiodegrade; see R. Sanghi, et al., Cassia angustifolia seed gum as aneffective natural coagulantfor decolourisation of dye solutions, GreenChem. 4 (2002) 252-254; T.A. Saleh, Isotherm, kinetic, and thermodynamicstudies on Hg (II) adsorption from aqueous solution by silica-multiwallcarbon nanotubes, Envir. Sci. Pollut. Res. 22 (2015) 16721-16731.

Many manufacturing processes lead to a discharge of effluents containingtoxic dyes that can cause ecological problems; see M. Thakur, et al.,Efficient photocatalytic degradation of toxic dyes from aqueousenvironment using gelatin-Zr (IV) phosphate nanocomposite and itsantimicrobial activity, Colloids Surf. B: Biointerfaces 157 (2017)456-463; and T.A. Saleh, Nanocomposite of carbon nanotubes silicananoparticles and their use for adsorption of Pb (H): from surfaceproperties to sorption mechanism, Desalin. Water Treat. 57 (2016)10730-10744.

Effluents from textile industries significantly contribute to waterpollution in part because dyes can undergo biological and chemicalchanges reacting with dissolved oxygen thereby leading to unhealthy andunstable aquatic ecosystems and the destruction of aquatic life.Moreover, the products of the degradation of many dyes are toxic andcarcinogenic. Therefore, the treatment of textile effluents before theirdisposal into the receiving water is important to save the environment.

Dyes can be removed from industrial wastewater in several ways includingby adsorption, coagulation, flotation, electrochemical techniques,biological treatments, and oxidation. However, most types of dyes, suchas neutral red, are soluble in aqueous solutions making manyconventional treatment methods ineffective for the removal of dyes fromwastewater.

One of the most effective methods for removing dyes is by adsorptionwhich is highly efficient, readily available and easy to handle.Adsorption is widely used and is a well-known process of separation fordealing with many types of chemical pollutants, particularly chemicalpollutants that are not removed by biological treatment of wastewater.Compared with other techniques, adsorption shows superior efficiency forthe removal of pollutants due to its simplicity, ease of operation, highefficiency, and insensitivity to inhibition by toxic pollutants or otherwastewater contaminants.

Contamination of water with metals such as Al, As, Ba, Cd, Cr, Cu, Fe,Pb, Mn, Hg, Se, and Ag is also a significant problem as high levels ofthese metals can negatively impact the environment and when ingestedcause a variety of medical and health problems. For example, arsenic iswidespread in the environment due to its natural occurrence and formerextensive use in pesticides. Symptoms of chronic arsenic poisoning areweight loss, hair loss, nausea, white lines across the toenails andfingernails, depression, and general fatigue. Cadmium poisoning has beenassociated with kidney disease, hypertension, and possibly geneticmutation. Chromium may cause lung tumors when inhaled and has adverseeffects on aquatic life. Mercury (Hg) poisoning results in weakness,loss of appetite, insomnia, indigestion, diarrhea, gum inflammation,loosening of the teeth, irritability, memory loss, muscle tremors, andbrain damage following large doses; and lead (Pb) is a cumulativepoison, meaning that it remains in the body following exposure. Childrenunder age three are most susceptible to lead poisoning. Minor symptomsinclude abdominal pains, decreased appetite, constipation, fatigue, anddecreased physical fitness. Long-term exposure may cause kidney damage,anemia, nerve and brain damage, and death.

While several types of adsorbents for use in various applications areunder development only some of these have been successfullycommercialized; see K. Zhu, et al, Cr(VI) reduction and immobilizationby core-double-shell structured magnetic polydopamine@zeolitic idazolateframeworks-8 microspheres, ACS Sustain. Chem. Eng. 5 (8) (2017)6795-6802; W. Yao, et al., Enhanced removal of methyl orange on calcinedglycerol-modified nanocrystallined Mg/Al layered double hydroxides,Chem. Eng. J. 307 (2017) 476-486; S. Yu, et al., Boron nitride-basedmaterials for the removal of pollutants from aqueous solutions: areview, Chem. Eng. J. 333 (2018) 343-360; A.M. Alansi, et al.,Visible-light responsive BiOBr nanoparticles loaded on reduced grapheneoxide for photocatalytic degradation of dye, J. Mol. Liq. 253 (2018)297-304; T.A. Saleh, et al., Kinetics, isotherms and thermodynamicevaluation of amine functionalized magnetic carbon for methyl redremoval from aqueous solutions, J. Mol. Liq. 248 (2017) 577-585; and N.

Tka, et al., Amines modified fibers obtained from natural Populustremula and their rapid biosorption of acid blue 25, J. Mol. Liq. 250(2018) 423-432.

There remains a strong demand for versatile adsorbents that cansimultaneously adsorb organic pollutants such as dyes as well as toxicmetals and which are easy and inexpensive to produce. Accordingly, theinventors sought to identify new ways for producing adsorbents withthese useful properties.

BRIEF SUMMARY OF THE INVENTION

A versatile adsorbent which is easy to make and can remove dyes andheavy metals from waste water is disclosed. This versatile adsorbent isconveniently produce by an innovative “single pot” interfacial reactionin which in situ formation of TiO₂ from a precursor occurs substantiallyat the same time as polymerization of a polyamide. As exemplifiedherein, the interfacial polymerization of trimesoyl chloride (TMC) and1,3-phenylene diamine (MPD) was simultaneously combined with the in-situformation of TiO₂ from TiCl₄ using urea. The structure and morphology ofthe resulting TiO₂-polyamide nanocomposite (TPN) was characterized.Surprisingly, it was found that the nanocomposite simultaneously removedorganic pollutants, such as dyes, as well as toxic metals, such as Ni,Cu, Pb, Se, As, Hg, Cd, and Cr, from waste water thus demonstrating theversatility of the nanocomposite for water treatment. Embodiments of theinvention include, but are not limited, to those described below.

One aspect of the invention is a method for producing a titania-polymernanocomposite comprising substantially simultaneously forming TiO₂nanoparticles in situ from a TiO₂ precursor in the presence of urea andinterfacially polymerizing polyamide precursors thereby producing atitania-polyamide polymer nanocomposite. In some embodiments of thismethod the TiO₂ precursor is TiCl₄. In other embodiments of this methodthe polyamide precursor comprises 1,3 phenylene diamine in an aqueousphase and trimesoyl chloride in a non-aqueous phase and/or the trimesoylchloride is dissolved in hexane under sonication. In some embodiments ofthis method the simultaneous forming comprises admixing 1,3 phenylenediamine, TiCl₄ and urea to form an aqueous solution, and mixing theaqueous solution with a non-aqueous solution of trimesoyl chloride; orthe trimesoyl chloride is added dropwise to the solution undercontinuous stirring for at least 1, 2, 3, 4, 5 or 6 hours, the resultingsolution is then heated to at least 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95 or >95° C. for 1, 1.5, 2, 2.5, 3, 3.5, 4, or >4hours, and then the titania-polymer is recovered by filtration andwashed to remove unreacted components.

In other embodiments of this method the trimesoyl chloride is addeddropwise to the solution under continuous stirring for at least 8, 12,16, 20, 24, 26, 28, or 30, preferably for at least 22-26 hours, theresulting solution is then heated to 45-55° C. preferably at 65-75° C.,for 1 to 8 hours, preferably for about 2-4 hours. The titania-polymer isrecovered, for example, by filtration, sedimentation or centrifugation,preferably by filtration, and can be washed one, two or more timesremove unreacted components.

Another embodiment of the invention is a titania-polymer nanocompositesuch as that produced by the methods disclosed herein. In someembodiments, this nanocomposite contains 10, 20, 30, 40, 50, 60, 70, 80,90 or >90 wt % TiO₂ the balance being polyamide. In other embodiments,the nanocomposite contains about 40-60 wt % TiO₂. In most or in typicalembodiments, the nanocomposite will be made by the method ofsimultaneous formation of TiO₂ and polymerization of a polyamidedisclosed herein.

In some embodiments, the composition contains a wt/wt ratio of TiO₂ topolymer, from about 4:1 to 10:1, from about 6:1 to 8:1 or about 7:1. Inother embodiments, the wt/wt ratio of TiO₂ to polymer ranges from about15:1 to 1:15, 10:1 to 1:10 or 7:1 to 1:7.

Another embodiment is directed to titania-polyamide nanocomposite thathas a BET surface area ranging from at least 55, 60, 65, 70, 75, 80, 85,90 to about 200, 150, or 100 m²g⁻¹ , preferably about 65-85 m²g⁻¹, amesopore surface area ranging from at least 30, 35, 40, 45, 50, 55, 60,65, 70 to 75 m²g⁻¹, preferably from about 43-63 m²g⁻¹, and a microporesurface area ranging from at least 10, 15, 20, 25, 30, 35, to 40 m²g⁻¹,preferably from about 15-30 m² g⁻¹. For example a nanocomposite may havea BET surface area ranging from about 65-85 m² g⁻¹, a mesopore surfacearea ranging from about 43-63 m²g⁻¹, and a micropore surface arearanging from about 15-30 m²g⁻¹ Another embodiment of the invention isdirected to water treatment apparatus that comprises a substrate towhich the titania-polyamide nanocomposite as disclosed herein has beenattached. Such a water treatment apparatus may comprise a bed containingthe titania-polyamide nanocomposite or that comprises a containercontaining contaminated water in which particles of thetitania-polyamide nanocomposite are circulated or otherwise mixed withcontaminated water. Such an apparatus typically includes a bed,preferably a fixed bed, filter or filter membrane containing the TiO₂polyamide nanocomposite disclosed herein to remove organic and metalliccontaminants.

It may further include one or more aerators, flocculators, sand filters,coaggulation aids such as polyelectrolytes, and sedimentation tanks orpools to remove solids. In some embodiments, contaminated water may betreated to remove oxidants such as chlorine, chloramine, bromine,oxygen, ozone etc.

In other embodiments, a bed, filter or filter membrane comprising thenanocomposite disclosed herein may be regenerated by removing boundmetals or organic compounds such as dyes, for example, by contacting itwith an acid or with a composition for regenerating such as a chemicalagent containing a water-dispersible resin, surfactant or organic acid,or an inorganic colloid. In some embodiments a regenerated TiO₂polyamide nanocomposite will regain at least 50, 60, 70, 80, 90, or 95%of its ability to bind to toxic metals and organic compounds such asdyes.

Another embodiment of the invention is directed to a method for removingat least one organic compound and/or a metal from contaminated water bycontacting the contaminated water with the titania-polyamidenanocomposite as disclosed herein. In some embodiments of this methodthe water is contaminated with the at least one organic compound and atleast one metal and the method simultaneously removes the organiccompound and metal at a temperature ranging from 10, 15, 20, 25, 30, 35,40, 45, 50 to >50° C., preferably from about 20-30° C. In someembodiments of this method the organic compound or metal is present inthe contaminated water at a concentration of no more than 25, 50, 75,100, 125, 150, 175, 200, 250, 300, 350, 400, 450 or 500 ppm, preferablyno more than 100 ppm. In other embodiments, the organic compound is atleast one dye such as methylene-blue or other phenothiazine-basedcompounds, bromophenol, methyl orange, Congo red and/or rhodamine B. Insome embodiments of this method the metal is selected from the groupconsisting of at least one of As, Se, Cu, Pb, Hg, Cd, Cr, and Ni ormixtures of two, three or more thereof..

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the invention and many of the attendantadvantages thereof will be readily obtained as the same becomes betterunderstood by reference to the following detailed description whenconsidered in connection with the accompanying drawings, wherein:

FIG. 1 is a graph illustrating the XRD diffractogram for (a)titania-Polyamide and (b) titania;

FIG. 2A. SEM image of TPN.

FIG. 2B. X-ray mapping of Ti and O in the TPN.

FIG. 2C. TEM image of the prepared TPN (FIG. 2C).

FIG. 2D. EDX spectrum with a table of EDX elemental analysis (FIG. 2D).

FIG. 3A is a graph illustrating the BET data of TPN: nitrogenadsorption/desorption isotherms.

FIG. 3B graph illustrating the BET data of TPN: pore size distributioncurve.

FIG. 4 is a graph illustrating the FTIR spectra of (a) polyamide and (b)titania-polyamide (TPN);

FIG. 5 is a scheme illustrating the color changes of the dye solutionsbefore and after the interaction with TPN; [experimental conditions:adsorbent mass 20 mg, volume 20 mL of each dye solution, contact time 60min, temperature 298 K];

FIG. 6 is a graph illustrating the effect of contact time on adsorptionof MB with solutions containing different TPN masses [Experimentalconditions; the amount of TPN: 5, 10 and 20 mg, medium volume: 30 mL,concentration of MB (16 ppm) and temperature: 298 K].

FIG. 7A plots of MB percentage removal versus time at differenttemperature. Experimental conditions; TPN amount: 20 mg, medium volume:30 mL, concentration of MB (16 ppm) and temperature: (i) 298 K, (ii) 318K, (iii) 338 K.

FIG. 7B plots In Kc versus 1/T. Experimental conditions; TPN amount: 20mg, medium volume: 30 mL, concentration of MB (16 ppm) and temperature:(i) 298 K, (ii) 318 K, (iii) 338 K.

FIG. 8 plots simultaneous removal of MB dye and toxic metals by TPN.

FIG. 9A illustrates the analysis of TPN after dye adsorption by FTIRspectrum.

FIG. 9B illustrates the analysis of TPN after dye adsorption by SEMimage.

FIG. 9C illustrates the analysis of TPN after dye adsorption by mappingof nitrogen indicating the distribution of the dye on the TPN adsorbent.

FIG. 10 illustrates the analysis of TPN after dye adsorption (a) FTIRspectrum, (b) SEM image, (c) mapping of nitrogen indicating thedistribution of the dye on the TPN adsorbent.

FIGS. 11 A, 11 B and 11 C. The plots of Lagergren's -first order (FIG.11 A), and pseudo-second order (FIG. 111B) and model of Interparticlediffusion at 298 K (FIG. 11C).

Experimental conditions: TPN weight: 20 mg, medium volume: 30 mL, MBinitial concentration (16 ppm) and temperature: 298 K.

FIGS. 12A, 12B and 12C. The plots of the experimental data usingIsotherm model of Langmuir (FIG. 12A), Isotherm model of Freundlich(FIG. 12B), Temkin adsorption isotherms (FIG. 12C). Experimentalconditions; TPN amount: 5.0, 10, 20 mg, medium volume: 30 mL,concentration of MB (16 ppm) and temperature: 298 K.

DETAILED DESCRIPTION OF THE INVENTION

The inventors sought to develop an adsorbent which has excellentproperties such as mechanical strength, rapid adsorption rate and a highcapacity for adsorption useful in treating wastewater. Another objectivewas to provide a simple method for producing a TiO₂ containingnanocomposite with these advantageous properties. As shown herein, theinventors achieved simultaneous combination of the interfacialpolymerization of trimesoyl chloride (TMC) and 1,3-phenylene diamine(MPD) with the in-situ formation of TiO₂ from TiCl₄. The inventors showthat combination of the titania with polyamide provided a composite thatis improved in comparison to conventionally formed TiO₂/polyamidecomposites and TiO₂ and polyamide individually. The N₂ physisorptionanalysis results indicated that the textural properties, like thesurface area of TPN, were improved compared with that of polyamide.X-ray mapping shows the efficient distribution of the titania within thepolymer structure. The TPN was evaluated for the adsorption of dyes andtoxic metals. The TPN showed good removal of several dyes in the orderof MB >bromo phenol > methyl orange > Congo red > rhodamine B. Kineticstudies were performed to understand the adsorption mechanism. Thekinetic studies indicated that the experimental data fit a second-ordermechanistic representation. The thermodynamic studies proved theapplicability of the TPN at room temperature since by increasing thetemperature the removal percentage decreased. Interestingly, TPN showedsimultaneous removal of MB dye and toxic metals including Se, As, Cu,Pb, Hg, Cd, Cr, and Ni. The prepared TPN composite was demonstrated tobe an efficient adsorbent for the simultaneous removal of dyes and toxicmetals.

Trimesoyl chloride is preferably used as a precursor to form thenanocomposite disclosed herein. In some alternative embodiments,trimesoyl chloride may be substituted with another polyamide formingprecursor such as trimesoyl-[4,4-dimethyl-5(4H)-azlactone].

Solvents. Preferably hexane is used as a solvent for TMC in the methodsas disclosed herein. Alternatively, other solvents such as benzene,cyclohexane, heptane, benzene, toluene, pentane, cyclopentane,1,4-dioxane, chloroform, diethyl ether or other non-polar solvents maybe substituted for hexane.

Daemines. Preferably 1,3 phenylene diamine is used to produce thenanocomnposite of the invention. In some alternative embodiments otherdiamines, compounds bearing two amine groups may be substituted for ormixed with 1,3 phenylene diamine. These include p-phenylenediamine (1,4,phenylene diamine), o-phenylenediamine (1,2 phenylene diamine),xylylenedia mines, such as m-xylylenediamine, p-xylylenediamine, oro-xylylenediamine, dimethyl-4-phenylenediamine, benzidine, and otheraromatic, linear or branched diamines that can polymerize with trimesoylchloride.

TiO₂ precursors include titanium(111) chloride-TiCl₃, titanium(IV)bromide (titanium tetrabromide)-TiBr₄, titanium(IV) chloride (titaniumtetrachloride)-Ti(Cl, and titanium(IV) iodide (titaniumtetraiodide)-TiI₄ The use of TiO₂ precursors permits formation of TiO₂in .sin in contrast to prior art methods that use ready or preformedTi,, it is not necessary to functionalize the Tio₂ produced by themethod disclosed herein, for example, with amine or other groups.

Alternative methods for producing nano TiO₂. Besides the methoddisclosed herein. nano TiO₂, may be synthesized by various other methodssuch as those described by Byranvand, et al. JNS (2013) 1-9; hypertexttransferprotocol://ns.kashanu.ac.ir/pdf_5436_20d28461e8600e7c915eab3d24924117.html(incorporated by reference). TiO₂ nanoparticles may also be produced bymechanical processes. Toxic metals include Al, As, Ba, Cd, Cr, Cu, Fe,Pb, Mn, Hg, Se, and Ag as well as those described at hypertext transferprotocol secure://_en.wikipedia.org/wiki/Heavy_metals (incorporated byreference, last accessed Aug. 1, 2019).

Water treatment or waste water treatment is any process that improvesthe quality of water to make it more acceptable for a specific end-use.The end use may be drinking, industrial water supply, irrigation, riverflow maintenance, water recreation or many other uses, including beingsafely returned to the environment. Water treatment removes contaminantsand undesirable components, or reduces their concentration so that thewater becomes fit for its desired end-use. This treatment is crucial tohuman health and allows humans to benefit from both drinking andirrigation use. Water to be treated includes ground water, rain water,condensates, water from rivers, lakes or streams, run-off water, andresidential, commercial or industrial waste water.

The concentration of a particular contaminant in water or waste, such asa toxic metal or organic compound, may be reduced to <100, 90, 80, 70,60, 50, 40, 30, 20, 10, 5, 2, 1, 0.5, 0.2, 0.1, 0.05, 0.02, 0.01 or<0.01% of its initial concentration by the methods disclosed herein.

The water purification methods described herein may be used, optionallyin conjunction with other processing or purification steps, to reducethe content of toxic metals and other contaminants to those meeting EPA,state, tribe, or local standards.

The U.S. Environmental Protection Agency (EPA) allows the followingconcentrations of toxic metals in waste: Ar (5.0 ppm), Ba (100.0 ppm),Cd (1.0 ppm), Cr (5.0 ppm), Pb (5.0 ppm), Hg (0.2 ppm), Se (10.0 ppm)and Ag (5.0 ppm). The methods disclosed herein may be used to lowertoxic metal concentrations to meet the above EPA standards or to furtherreduce toxic metal concentrations below what is required by thesestandards, for example, by further reductions to <100, 90, 80, 70, 60,50, 40, 30, 20, 10, 5, 2, 1, 0.5, 0.2, 0.1, 0.05, 0.02, 0.01 or <0.01%of its EPA permissible concentration in waste or to meet EPA drinkingwater standards EPA drinking water standards (goal or maximumcontaminant level) for these and other contaminants are incorporated byreference to hypertext transfer protocolsecure://www.epa.gov/ground-water-and-drinking-water/national-primary-drinking-water-regulations(last accessed Aug. 2, 2019). For example, for As (goal: 0 mg/mL andMCL: 0.010 mg/L: goal/MCL), for Ba (2 mg/L), for Cd (0.005 mg/L), for Cr(0.1 mg/L), for Pb (goal: 0 mg/mLand MCL: 0.015 mg/L), Hg (0.002 mg/L),and Se (0.05 mg/L) where MCL is maximum contaminant level.

EPA secondary MCL standards for drinking water for Al are 0.05 to 0. 2mg/L, for Cu 1.0 mg/L, for Fe 0.3 mg/L, for Mn 0.05 mg/L, 0.1 mg/L forAg and for Zn 5 mg/L. The methods disclosed herein may be used to reduceAl, Cu, Fe, Mn or Zn in water to meet these secondary drinking waterstandards or to exceed them by further reductions to <100, 90, 80, 70,60, 50, 40, 30, 20, 10, 5, 2, 1, 0.5, 0.2, 0.1, 0.05, 0.02, 0.01 or<0.01% of the permissible concentrations. Secondary EPA MCL standardsfor metals and other contaminants are incorporated by reference tohypertext transfer protocolsecure://www.epa.gov/dwstandardsregulations/secondary-drinking-water-standards-guidance-nuisance-chemicals(last accessed Aug. 2, 2019).

Filters, membranes. The TiO₂ polyamide nanocomposite (TPN) of theinvention may be formulated as a membrane, such as a filter membrane,membrane/deep filter combination, filter body, or reverse osmosismembrane. In some embodiments, a pore forming agent such as an ethyleneglycol may be incorporated into the nanocomposite during synthesis of afilter or filter membrane. In some alternative embodiments the TPN maybe formulated as nanoparticles or microparticles, as a bed of TPNparticles, as a substrate coated with TPN, or as a substrate materialinto which TPN has been incorporated.

Regeneration. In some embodiments, once used to adsorb metals or organicmolecules such as dyes, the nanocomposite may be regenerated andrecycled for subsequent use as an adsorbent, for example, contacting afilter, membrane, bed or other material comprising the TiO₂ polyamidenanocomposite disclosed herein with 0.25, 0.5, 0.75, 1, 1.25, 1.5, 1.75,or 2M nitric acid or another acid which permits elution of a bound heavymetal or an organic solvent such as acetone, methyl ethyl ketone, methylacetate, or so-called green acetones such as Replacatone™ (hypertexttransfer protocol secure://www.tapplastics.com/uploads/pdf/MSDS%20Replacetone.pdf, incorporated by reference, last accessed Aug. 2,2019) or BioSolv™ (hypertext transfer protcolsecure//syndel.com/wp-content/uploads/2019/02/Biosolve-SDS.pdf,incorporated by reference, last accessed Aug. 2, 2019) to remove anorganic component such as a dye from the nanocomposite and optionallywashing the nanocomposite prior to reuse. TPM can also be regeneratedusing a solvent comprising nitric acid, acetone and other organissolvents.

Other applications. Besides use of the titania-polyamide nanocomposite(TPN), or water treatment apparatuses or water filters for removal oforganic contaminants such as dye, or heavy metals, it may beincorporated into coatings and other materials to provide UV resistance,self-cleaning coatings or materials, inks, cosmetics, paper, plastics,special functional coatings such as magnetic coatings, clothing orfibers including masks, gloves and other protective gear, air and waterfilters including nanofiltration membranes, and antiseptic andantimicrobial products.

Examples

Chemicals including titanium chloride (molecular weight of 189.68 g/moland purity of 99%), hexane (molecular weight of 86.18 g/mol and purityof 99%), urea (molecular weight of 63.05 g/mol and purity of 98%), andtrimesoyl chloride, C₉H3Cl₃O₃, (TMC) (molecular weight of 265.47 g/mol,and purity of 98%) were purchased from Sigma Aldrich. 1,3 Phenylenediamine, C₆H₄(NH₂)₂, (MPD) (molecular weight of 108.14 g/mol and purityof 98%) was purchased from Fluka.

Synthesis of materials. The titania-polymer nanocomposite (TPN) wassynthesized by in situ interfacial polymerization which wassimultaneously combined with the in-situ formation of TiO₂ from TiCl₄using urea.

About 100 mL de-ionized water was used to dissolve 2 g of 1,3 phenylenediamine. 20 mL of TiCl₄ was then added to the phenylene diaminesolution.

Then 1.5 g of urea was added and stirred for 10 min.

On the other side, 50 mL hexane was used for dissolving 0.2 g oftrimesoyl chloride by sonication.

This solution was added dropwise to the previous mixture undercontinuous stirring.

After that, the complete mixture was kept under stirring for about 24 h,then it was heated at 70° C. for 3 h.

The obtained composite was filtered and washed to remove any unreactedcomponents.

For the purpose of comparison, both pure titania and pure polyamide werealso prepared. The polyamide was prepared by following the same stepswithout adding TiCl₄ and the titanium oxide was prepared by thefollowing steps: TiCl₄ of volume 50 mL was added slowly to distilledwater (200 mL) in an ice bath, after that the beaker was transferred toroom temperature. The beaker was kept under stirring for 30 min and theurea (1.5 g) was dissolved in water and then added. The bath temperatureincreased to 150° C. which was maintained. Urea was added to thesolution to enhance the formation of hydroxides. The solution becamewhite colloidal without precipitation, then the solution reaction wasleft to settle, cool and finally washed 3 times with distilled water.

Characterization and analysis. A scanning electron microscope (SEM) wasused to describe the morphology of TPN. An X-Max detector fitted withenergy-dispersive X-ray spectroscopy (EDX) was used for the elementalanalysis. X-ray mapping was used to illustrate the distribution oftitania on the surface of the TPN.

The X-ray powder diffraction (XRD)diffractogram was obtained using anX-ray diffractometer through radiation of Cu-Kα.

The BET surface area was measured on a Micromeritics TriStar II Plusautomatic analyzer using N₂ adsorption-desorption at −196° C. Prior tomeasurement, the sample was degassed at 150° C. for 3 hr to removeimpurities or moisture. The Brunauer, Emmett, and Teller (BET) methodwere used to calculate the surface area. A Thermo Scientific FTIRspectrometer was used to perform IR measurements with a deuteratedtriglycine sulfate detector. Spectra background corrections were done ata resolution of 2 cm¹ and 32 scans were made.

A UV-vis spectrophotometer with optical quartz cuvettes was used tomonitor the dye concentrations.

An Inductively Coupled Plasma Mass Spectrometer (ICP-MS) was used toanalyze the concentration of metal ions in the samples.

Adsorption evaluation. A methylene blue (MB) dye solution with aconcentration of 16 ppm was prepared. The initial pH of the solution was6. Then, TPN was added and the contents were stirred for various periodsand at different temperatures. Then, at different intervals, aliquotswere collected and analyzed using UV-vis spectrophotometer at X of 665nm. The removal percentage of the dyes was then calculated. Severalfactors were investigated including dosage or concentration, contacttime, temperature and interference effect.

For evaluating dosage, the initial concentration of the dye was keptconstant, 16 ppm.

Different dosages of the TPN were used. Then experiments at differenttemperatures of 29., 318 and 33$ K were done to describe thethermodynamic and kinetic parameters.

The interference effect was studied using 20 mg of adsorbent in 16 ppmdye solution spiked with I ppm of metals including Ni, Cu, Pb, Se, As,Hg, Cd, and Cr.

The adsorption capacity and removal percentage of the adsorbent iscomputed using Eqs. (1) and (2):

$\begin{matrix}{q_{t} = \frac{\left( {C_{i} - C_{t}} \right)V}{W}} & (1)\end{matrix}$ $\begin{matrix}{{{Removal}{efficiency}(\%)} = {\left( \frac{C_{i} - C_{t}}{C_{i}} \right) \times 100}} & (2)\end{matrix}$

where, C_(i) and C_(t) represent concentrations of methylene blue (MB)(initial and final, respectively), V and W denote the volume of solution(L) and material weight (g). The capacity of adsorption at differenttimes and equilibrium are expressed as q_(i), and g_(e), respectively,where in the case of q_(t). the equilibrium concentration Ct is usedinstead of (C_(t), The analysis was done in triplicate and the averagevalue was taken.

TABLE 1 The BET parameters of TPN and polyamide. Parameter TPN PolyamideTotal pore volume 0.13 cm³ · g⁻¹ 0.12 cm³ · g⁻¹ Micropore volume 0.14cm³ · g⁻¹ 0.15 cm³ · g⁻¹ Average pore diameter 94.4 Å 82 Å Mesoporesurface area 53.1 m² · g⁻¹ 7 m² · g⁻¹ Micropore surface area 22.5 m² ·g⁻¹ 3 m² · g⁻¹ BET surface area 75 m² · g⁻¹ 10 m² · g⁻¹

Characterizations of the samples From the XRD diffractogram. there arecharacteristic peaks of titania nanoparticles that can be observed at2θof 25.3° 38.2°, 47.9°,54.2°, 64.3°and 77.1°, as shown in FIG. 1 Also,there is a characteristic peak of the polymer at 18.6°. Peaks at 2θ of8.4° and 20.7° are related to the TPN structure clarifying itscrystalline nature. These results confirmed the successful embedding oftitanium oxide into the polyamide during the formation of TPN.

FIG. 2A illustrates the SEM image indicating the morphology of thesample in which the nanoparticles are embedded. The EDX in FIG. 2Ddescribes the presence of elements which can be observed at 0.277 forcarbon, 0.392 for nitrogen and 0.525, 4.5 and 4.9 keV for titanium. Thenitrogen peak is overlapped with the oxygen and titanium peaks. Thespectrum clarifies a set of peaks for titanium represented by 15.87 wt %and 36.49 for Ti and O, respectively. This wt % indicates that titaniumoxide is embedded successfully inside the polyamide.

FIG. 2B depicts the X-ray mapping which shows the dispersion of titaniananoparticles within the polymer. As shown in the mapping images fortitanium, there is a uniform distribution of the nanoparticles insidethe composite.

This was confirmed by the TEM image FIG. 2C, which shows the formationof titania particles within the polymer.

TABLE 2 Kinetic parameters of dye adsorption on the TPN; C_(i) (16 ppm)Lagergren's first order Pseudo-second order Intraparticle diffusionq_(e), exp. k₁ q_(e), cal q_(e), cal C (mg/g) (min⁻¹) (mg/g) R² k₂ ^(a)(mg/g) R² k_(id) ^(b) (mg/g) R² 22.7 0.052 6.78 0.64 0.0112 23.1 0.9980.163 1.36 0.976

The N₂-physisorption analysis was performed to investigate the texturalproperties of TPN. FIG. 3A depicts the BET isotherm plot which indicatesthat the isotherm belongs to type II with uniform surface energy andmultilayer adsorption. The uptake of nitrogen at relatively lowpressures gives an indication for the sample with a microporousstructure. The mesoporous structure of TPN has been confirmed by a loopof hysteresis at a pressure that is relatively high. Other parametersobtained from the analysis were summarized in Table 1.

The BET surface area of the TPN nanocomposite is shown to be 75 m²/gcompared with 10 (m²/g) of the polymer. The pore size distributionindicated that the TPN material has a size in the range of 20-100 nm, asshown in FIG. 3B.

FIG. 4 illustrates the FTIR spectra of polyamide and TPN composite. Thebroad band observed in the range of 3300-3500 cm-¹ was attributed to N-Hstretching vibration of 1,3 phenylenediamine. The peaks recorded at 2920cm-¹ and 2850 cm-¹ were related to C-H stretching vibration. Anotherabsorption band for C═O stretching vibration appeared at 1620cm⁻¹.

Evaluation of dye adsorption efficiency. The adsorption efficiency ofthe prepared TPN material was tested using different dyes. The dyesolutions were prepared separately, and 20 mg TPN was added to each ofthem. The contact time was allowed until equilibrium was obtained. Theconcentration of the dye was determined by a UV-vis spectrophotometer.It was found that the performance of the TPN differs from one dye toanother depending on the nature and the structural size of the dyes. Thepercentage removal of the dyes over the TPN was found to be in thefollowing order of methylene blue >bromo phenol >methyl orange >Congored >rhodamine B, FIG. 5 . For MB, the removal was ˜100% so it waschosen for further investigation. It should be also mentioned that theadsorption efficiency of TPN, titania, and polyamide was tested underthe same conditions. TPN showed better efficiency than both titania andpure polyamide because TPN composite combines the properties and thefunctional groups of both titania and polyamide. This allows having moreactive sites for adsorption.

Contact time. Different dosages of TPN (5, 10, and 20 mg) were added todye solutions (30 mL each) having an initial concentration of 16 ppm. Inthese batch experiments, the dependence of the adsorption capacity oncontact time at a room temperature of 298 K was evaluated, The fast dyeadsorption rate with steep slopes indicates that the adsorptionequilibrium was obtained within 20 min as shown in FIG. 6 . This fastuptake makes the TPN promising for its use in real treatments.

Adsorption kinetics. Kinetic models of pseudo-second order andLagergren's first order were used for examining the adsorptionmechanisms, Linear Eq. (3) was used for the first order model.

In(q_(e)−q_(t))=Inq_(e)−k_(t)t  (3)

where the dye amount (mg. g⁻¹) is adsorbed at equilibrium and r whichare represented by q, and q, respectively, while the rate constant isrepresented by k_(l) q_(e) and k_(l) values were obtained by plottingln(q_(e)−q_(t)) versus/as shown in FIG. 11A and Table 2. The poorcorrelation coefficients (R²) and the disagreement between thecalculated values of (q_(e), cal) and the experimental (q_(e), exp),gives an indication that the adsorption rate does not correlate with thefirst-order model When studying the second-order rate of adsorption, thefollowing Eq. (4) was used:

$\begin{matrix}{\frac{{dq}_{t}}{dt}{k_{2}\left( {q_{e} - q_{t}} \right)}^{2}} & (4)\end{matrix}$

where the rate constant is represented by k₂, q_(l), and q_(e), are thecapacities of adsorption at time t and at equilibrium The linear form ofthe pseudo-second-order is described as the following:

$\begin{matrix}{\frac{t}{q_{t}} = {\frac{1}{k_{2}q_{e}^{2}} + \frac{t}{q_{e}}}} & (5)\end{matrix}$

where the rate constant value k₂ is obtained from the plot of t/q_(t)versus t as shown in FIG. 11B, There is an agreement between q_(e), expand the q_(e) cal and the high correlation coefficient values clarifiedthat the process of adsorption fitted to the pseudo-second-order model.This is an indication that the dye ions adsorption possibly occurred viaa predominantly chemical interaction.

Weber's intraparticle diffusion model was used for fitting theadsorption results by using Eq. (6):

q_(t)=K_(kt)t^(1/2)+C  (6)

where the rate constant of intraparticle diffusion is represented by ak, (mg-g min), and the intercept (mg, ^(g−1)) is C. As per theexperimental data, the linearity varies to some extent when plotting q,versus /” which indicates the rate-limiting step by intraparticlediffusion.

As shown in FIG. 11C, the intraparticle diffusion is represented bylinear portions. The external surface adsorption is the first stage andwas completed within the first min The second stage represents theintraparticle diffusion stage known as the rate determining step.

This stage was observed, in <20 min. The plot contains a. third regionwhere the interparticle diffusion begins to diminish. The linear line ofthe second stage didn't intercept with the origin point because thefinal and initial stages of the adsorption process have a different masstransfer rate indicating that the interparticle diffusion wasn't theonly rate limiting step.

TABLE 3 Isotherm parameters of Langmuir, Freundlich, and Temkin for thedyes adsorption Langmuir Freundlich Temkin q_(m) k_(L) k_(f) K_(r) b_(r)(mg/g) (L/mg) R_(L) R² 1/n n (mg/g) R² (L/g) (KJ/mol) R² 43 0.833 0.130.9606 0.22 4.59 3.13 0.9254 1.004 0.383 0.8775

Adsorption isotherms. A good analysis of adsorption capacities wasconducted using isotherm models with fundamental physicochemical data.The Isotherm model of Langmuir is based on the idea. of a homogenousmonolayer surface phase. The nature of the process, either chemical orphysical, can be described through it:

$\begin{matrix}{\frac{C_{e}}{q_{e}} = {\frac{1}{k_{L}q_{m}} + \frac{C_{e}}{q_{m}}}} & (7)\end{matrix}$

where k_(L) (L ·mg⁻¹), q_(m)(mg·g⁻¹) q_(e) (mg·g⁻¹) and C_(e) (mg·L⁻¹)clarify the sites of adsorption affinity; the theoretical monolayeradsorption capacity, the amount adsorbed. of MB and its equilibriumconcentration, respectively.

FIG. 12A shows the C_(e)/q_(e) versus C_(e) plot, where the k_(L) andLangmuir constant q_(m)v values are obtained from the slope andintercept, shown in Table 3. The dimensionless equilibrium parameterR_(L) is given in Eq. (8):

$\begin{matrix}{R_{L} = \frac{1}{1 + {K_{L}C_{O}}}} & (8)\end{matrix}$

where the initial solute concentration is C, R_(t) is the equilibriumfactor and indicates the adsorption, if R_(L)=1 linear. R_(L) >1unfavorable, <R_(L) <1 favorable and R_(L)=0 irreversible. Theadsorption favorability by the R_(L) value of 0. 13 was confirmed TheTPN adsorption capacity (q,) and other parameters are listed in Table 3.

Heterogeneous surfaces and their adsorption characteristics wereillustrated by the Freundlich model considering the interactions ofadsorbed molecules, as:

q _(e) =K _(t) C _(e)  (9)

K_(f) (mg·g⁻¹) represents the constant of the Freundlich isotherm andI/n describes the capacity of adsorption and its intensity, respectivelyThe adsorbate concentration (mgL⁻¹) and the amount adsorbed (mg g⁻¹) atequilibrium are represented by C, and q, The model is:

$\begin{matrix}{{\ln q_{e}} = {{\ln K_{t}} + {\frac{1}{n}\ln C_{e}}}} & (10)\end{matrix}$

The plot In q_(e) versus In C_(e) is used to calculate the values ofK_(F) and n as shown in FIG. 12B and included in Fable 3. The nature ofthe adsorption processes is described by the n value where: 1/n<1 and >1imply a cooperative and a normal adsorption, respectively. The obtainedresults indicate the 1/n value of ≈0.22, A linear decrease in adsorptionenergy due to the interaction between adsorbent and adsorbate is assumedby the Temkin model and given as:

$\begin{matrix}{q_{e} = {{\frac{RT}{b_{T}}\ln k_{T}} + {\frac{RT}{b_{T}}\ln C_{e}}}} & 11\end{matrix}$

where b_(T) represents the Temkin isotherm constant and shows thesorption heat (J/mol), while k_(T) represents the binding constant ofthe Temkin isotherm equilibrium which describes the highest energybinding (L·g⁻¹). T and R are representing the temperature (K) and gasconstant, respectively. The isotherm constants are obtained by plottingthe q_(e) versus the In C_(e), as shown in FIG. 12C.

Thermodynamic study. Thermodynamic adsorption parameters such as freeenergy (ΔG°). enthalpy (ΔH° ) and the entropy (Δ) can be determined toillustrate the process of adsorption and are evaluated using thefollowing Eqs. (12), (13), (14) and (15).

$\begin{matrix}{K_{c} = {C_{Ae}/C_{e}}} & (12)\end{matrix}$ $\begin{matrix}{{\Delta G{^\circ}} = {{- {RT}}\ln K_{c}}} & (13)\end{matrix}$ $\begin{matrix}{{\Delta G{^\circ}} = {{\Delta H{^\circ}} - {T\Delta S{^\circ}}}} & (14)\end{matrix}$ $\begin{matrix}{{\log k_{2}} = {\frac{E_{a}}{2.303{RT}} - {constant}}} & (15)\end{matrix}$

After carrying out the adsorption processes at three differenttemperatures of 298 K, 318 K, and 338 K, it was found that the removalrate decreases as the temperature of adsorption increases, as shown inFIG. 7 . The Van't Hoff equation is used to obtain the InKc versus 1/Tplot in the linear form gave the ΔH° and ≢S° values which can be used tocompute the ΔG° using Eq. (14):

$\begin{matrix}{{\ln K_{c}} = {{- \frac{\Delta H{^\circ}}{RT}} + \frac{\Delta S{^\circ}}{R}}} & (16)\end{matrix}$

The MB adsorption on TPN was found to be exothermic. The adsorptionthermodynamic parameters were calculated. The AG° values were in therange of −0.8.4 (KJ/mol) for 298 K, −5,5 (J/mol) for 318 K and to −2,6(kJ/mol) for 348 K. These values clarified, the exothermic behavior forthe process of adsorption. As the temperature increases, there is adecrease in the absolute values ofΔG° which indicates that theadsorption of the dye on TPN is an unfavorable process.

On the other side, the negative value of enthalpy ΔH° which is≈−51kJ/mol shows the adsorption as an exothermic process, while thenegative value of the entropy ΔS° of −140 J/mol K reflects the lowaffinity of the adsorbent toward the pollutant molecules at hightemperature.

Metals interference effect and recycling: Industrial contaminationcontains many pollutants which are classified into organic and inorganiccomponents. The process of dye adsorption may be affected by thepresence of heavy metals, so it is necessary to investigate theinfluence of the components. Thus, the removal of MB was performed inthe presence of several metals; As, Se, Cu, Pb, -g, Cd, Cr, and Ni.Then, the dye concentration was analyzed using a UV-visspectrophotometer and the metals were analyzed using ICP-MS. As shown inFIG. 8 , the results indicated. that the TPN adsorbed almost 98% thedye.

In addition, metals like As, Se, Cu, Pb, and Hg were highly co-adsorbedby TPN.

This indicates that the TPN has a high efficiency toward cationicspecies. FIG. 9A illustrates the analysis of TPN after dye adsorption byFTIR spectrum. FIG. 93 illustrates the analysis of TPN after dyeadsorption by SEM image and FIG. 9C illustrates the analysis of TPNafter dye adsorption by mapping of nitrogen indicating the distributionof the dye on the TPN adsorbent. The analysis of the adsorbent after dyeadsorption was conducted to understand the nature of the interaction. Asshown in FIG. 9B, the morphology has not been changed significantly,however, the FTIR spectrum shown more bands as a result of dye adsorbentinteraction. As the nitrogen is part of the methylene blue, the nitrogenmapping was conducted and the image indicated that the dye was dispersedon the TPN. The decrease in the affinity of adsorption of some metalscould be due to the simultaneous removal of many metals along with thedye. There could be a metal-dye interaction as proposed in the mechanismshown in FIG. 10 . Thus, the electrostatic interactions cannot be theonly adsorption force, and other complex and varying kinds ofinteractions could be involved in the adsorption. Possible mechanismsfor the adsorption are proposed in FIG. 10 , including the 7L-7Linteraction and the electrostatic interaction. In addition, acomplexation interaction between MB and metals could take place, whichcan be explained by the high adsorption of MB and the metal ions.

The possibility to recycle the adsorbents, which is important to theindustry, was also studied. The spent adsorbent was treated with acetoneto dissolve dye and then was treated with a 1 M solution of nitric acidto desorb the metals. The mixture then filtered and the collect TPNadsorbent was dried and reused for the adsorption of the dye and metalswhich showed almost the same performance with standard deviation, i.e.experimental errors of 5%.

The filtrate containing the metals was treated with NaOH to precipitatethe metals in metal hydroxide solid form.

As disclosed herein, interfacial polymerization of trimesoyl chloride(TMC) and 1,3-phenylene diamine (MPD) was simultaneously combined withthe in-situ formation of TiO₂ from TiCl₄ using urea. Thetitania-polyamide nanocomposite (TPN) produced was characterized byusing X-ray diffraction, Fourier transform infrared spectroscopy,N₂-physisorption analysis and a scanning electron microscope equippedwith energy-dispersive X-ray spectroscopy.

The TPN was evaluated as an adsorbent for the removal of dyes and showedhigh efficiency for the removal of several dyes in the order: methyleneblue >bromo phenol >methyl orange >Congo red >rhodamine B. The dosage,contact time, and temperature which are the main factors that affectadsorption efficiency were determined.

Among isotherm models, the experimental adsorption results fitted wellwith the Langmuir model with a maximum adsorption capacity of 43 mg/g.Kinetic experiments were conducted to describe the equilibrium rate. Themodel of the pseudo-second-order adequately fitted the experimental datawith a correlation coefficient R² of 0.998.

Thermodynamic studies were performed to evaluate the performance of TPNat various temperatures. Thus, parameters including free energy (AG° ),enthalpy (AH° ) and the entropy (ΔS° ) were calculated. The influence ofthe interference on adsorption was investigated in the presence ofmetals including Ni, Hg, As, Cu, and Cr.

Surprisingly, with ≈100% removal of the dye, TPN showed a rapidsimultaneous uptake of the toxic metals as well.

Terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the invention.

The headings (such as “Background” and “Summary”) and sub-headings usedherein are intended only for general organization of topics within thepresent invention, and are not intended to limit the disclosure of thepresent invention or any aspect thereof. In particular, subject matterdisclosed in the “Background” may include novel technology and may notconstitute a recitation of prior art. Subject matter disclosed in the“Summary” is not an exhaustive or complete disclosure of the entirescope of the technology or any embodiments thereof. Classification ordiscussion of a material within a section of this specification ashaving a particular utility is made for convenience, and no inferenceshould be drawn that the material must necessarily or solely function inaccordance with its classification herein when it is used in any givencomposition.

As used herein, the singular forms “a”, “an” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise.

It will be further understood that the terms “comprises” and/or“comprising,” when used in this specification, specify the presence ofstated features, steps, operations, elements, and/or components, but donot preclude the presence or addition of one or more other features,steps, operations, elements, components, and/or groups thereof.

As used herein, the word “include,” and its variants, is intended to benon-limiting, such that recitation of items in a list is not to theexclusion of other like items that may also be useful in the materials,compositions, devices, and methods of this technology. Similarly, theterms “can” and “may” and their variants are intended to benon-limiting, such that recitation that an embodiment can or maycomprise certain elements or features does not exclude other embodimentsof the present invention that do not contain those elements or features.

As used herein, the term “and/or”includes any and all combinations ofone or more of the associated listed items and may be abbreviated as“/”.

Links are disabled by spelling out of or deletion of “http” or byinsertion of a space or underlined space before www. In some instances,the text available via the link on the “last accessed” date may beincorporated by reference.

As used herein in the specification and claims, including as used in theexamples and unless otherwise expressly specified, all numbers may beread as if prefaced by the word “substantially”, “about” or“approximately,” even if the term does not expressly appear. The phrase“about” or “approximately” may be used when describing magnitude and/orposition to indicate that the value and/or position described is withina reasonable expected range of values and/or positions. For example, anumeric value may have a value that is +/−0.1% of the stated value (orrange of values), +/−1% of the stated value (or range of values), +/−2%of the stated value (or range of values), +/−5% of the stated value (orrange of values), +/−10% of the stated value (or range of values),+/−15% of the stated value (or range of values), +/−20% of the statedvalue (or range of values), etc. Any numerical range recited herein isintended to include all sub-ranges subsumed therein.

Disclosure of values and ranges of values for specific parameters (suchas temperatures, molecular weights, weight percentages, etc.) are notexclusive of other values and ranges of values useful herein. It isenvisioned that two or more specific exemplified values for a givenparameter may define endpoints for a range of values that may be claimedfor the parameter. For example, if Parameter X is exemplified herein tohave value A and also exemplified to have value Z, it is envisioned thatparameter X may have a range of values from about A to about Z.Similarly, it is envisioned that disclosure of two or more ranges ofvalues for a parameter (whether such ranges are nested, overlapping ordistinct) subsume all possible combination of ranges for the value thatmight be claimed using endpoints of the disclosed ranges. For example,if parameter X is exemplified herein to have values in the range of 1-10it also describes subranges for Parameter X including 1-9, 1-8, 1-7,2-9, 2-8, 2-7, 3-9, 3-8, 3-7, 2-8, 3-7, 4-6, or 7-10, 8-10 or 9-10 asmere examples. A range encompasses its endpoints as well as valuesinside of an endpoint, for example, the range 0-5 includes 0, >0, 1, 2,3, 4, <5 and 5.

As used herein, the words “preferred” and “preferably” refer toembodiments of the technology that afford certain benefits, undercertain circumstances. However, other embodiments may also be preferred,under the same or other circumstances. Furthermore, the recitation ofone or more preferred embodiments does not imply that other embodimentsare not useful, and is not intended to exclude other embodiments fromthe scope of the technology.

As referred to herein, all compositional percentages are by weight ofthe total composition, unless otherwise specified.

Although the terms “first” and “second” may be used herein to describevarious features/elements (including steps), these features/elementsshould not be limited by these terms, unless the context indicatesotherwise. These terms may be used to distinguish one feature/elementfrom another feature/element. Thus, a first feature/element discussedbelow could be termed a second feature/element, and similarly, a secondfeature/element discussed below could be termed a first feature/elementwithout departing from the teachings of the present invention.

The description and specific examples, while indicating embodiments ofthe technology, are intended for purposes of illustration only and arenot intended to limit the scope of the technology. Moreover, recitationof multiple embodiments having stated features is not intended toexclude other embodiments having additional features, or otherembodiments incorporating different combinations of the stated features.Specific examples are provided for illustrative purposes of how to makeand use the compositions and methods of this technology and, unlessexplicitly stated otherwise, are not intended to be a representationthat given embodiments of this technology have, or have not, been madeor tested.

All publications and patent applications mentioned in this specificationare herein incorporated by reference in their entirety to the sameextent as if each individual publication or patent application wasspecifically and individually indicated to be incorporated by reference,especially referenced is disclosure appearing in the same sentence,paragraph, page or section of the specification in which theincorporation by reference appears.

The citation of references herein does not constitute an admission thatthose references are prior art or have any relevance to thepatentability of the technology disclosed herein. Any discussion of thecontent of references cited is intended merely to provide a generalsummary of assertions made by the authors of the references, and doesnot constitute an admission as to the accuracy of the content of suchreferences.

1. (canceled)
 2. The titania-polyamide nanocomposite of claim 8, whereinthe method of making the titania-polyamide nanocomposite the TiO₂precursor is TiCl₄.
 3. The titania-polyamide nanocomposite of claim 8,wherein the method of making the titania-polyamide nanocomposite thepolyamide precursor comprises 1,3 phenylene diamine in an aqueous phaseand trimesoyl chloride in a non-aqueous phase.
 4. The titania-polyamidenanocomposite of claim 8, wherein the method of making thetitania-polyamide nanocomposite; the trimesoyl chloride is dissolved inhexane under sonication.
 5. (canceled)
 6. The titania-polyamidenanocomposite of claim 8, wherein the method of making thetitania-polyamide nanocomposite the trimesoyl chloride is added dropwiseto the solution under continuous stirring for at least 4 hours, theresulting solution is then heated to at least 50° C. for 2 hours ormore, and then the titania-polymer is recovered by filtration and washedto remove unreacted components.
 7. The titania-polyamide nanocompositeof claim 8, wherein the method of making the titania-polyamidenanocomposite the trimesoyl chloride is added dropwise to the solutionunder continuous stirring for at least 22-26 hours, the resultingsolution is then heated to at 65-75° C. for 2-4 hours, thetitania-polymer is recovered by filtration, and then washed to removeunreacted components.
 8. A titania-polyamide nanocomposite made by amethod comprising: simultaneously forming TiO₂ nanoparticles in situfrom a TiO₂ precursor in the presence of urea and interfaciallypolymerizing polyamide precursors thereby producing a titania-polyamidenanocomposite, wherein the simultaneous forming comprises: admixing1,3-phenylene diamine, TiCl₄ and urea to form an aqueous solution, andmixing the aqueous solution with a non-aqueous solution of trimesoylchloride.
 9. (canceled)
 10. The titania-polyamide nanocomposite of claim8 that is 10-90 wt % TiO₂ and about 90 to 10 wt % polyamide.
 11. Thetitania-polyamide nanocomposite of claim 8 that is 40-60 wt % TiO₂ andabout 60 to 40 wt % polyamide.
 12. The titania-polyamide nanocompositeof claim 8 that has a BET surface area ranging from 65-85 m²·g⁻¹, amesopore surface area ranging from about 43-63 m²·g⁻¹, and a microporesurface area ranging from about 15-30 m²·g⁻¹.
 13. (Currently Amended).The titania-polyamide nanocomposite of claim 8 that has a BET surfacearea ranging from 65-85 m²·g⁻¹, a mesopore surface area ranging fromabout 43-63 m²·g⁻¹, and a micropore surface area ranging from about15-30 m²·g⁻¹.
 14. (canceled)
 15. (canceled)
 16. (canceled) 17.(canceled)
 18. (canceled)
 19. (canceled)
 20. (canceled)
 21. Thetitania-polyamide nanocomposite of claim 8 that is in the forn of aporous membrane comprising ethylene glycol.
 22. The titania-polyamidenanocomposite of claim 8, having a total pore volume of 0.13 cm³/g, amicropore volume of 0.14 cm³/g, an average pore diameter of 94.4 Å, amesopore surface area of 53.1 m²/g, a micropore surface area of 22.5m²/g, and a BET surface area of 75 m²/g.
 23. The titania-polyamidenanocomposite of claim 8, having 20 peaks in the XRD diffractogram at8.4°, 18.6°, 20.7°, 25.3°, 38.2°, 47.9°, 54.2°, 64.3° and 77.1°.